Synthetic resins



- 45 temperature does not exceed 90 Patented May 31, 1932 PATENT OFFICE LEO BOSENTHAL, OF VOHWINKEL, NEAR ELIBERFELD,

,enamnv, ASSIGNOB To to.

FARIBENINDUSTRIE AK'IIENGESELLSCEAFT, OF FBANKFORT-OK-THE-MAIN, GER- MANY, A conrormrrori or Grammy SYNTHETIC BEGINS 1T0 Drawing. Application filed June 25, 1929, Serial No. 373,884, and in Germany July 2,

R" OR wherein R and R stand for alkyl groups which may be similar or dissimilar to one another and R stands for'hydrogen which may be substituted by an alkyl group. Suitable for the purpose of the invention are all the catalysts generally used in the manufacture of cunrarone resins (compare: The Journal of Industrial and Engineering Chemistry, vol. 8, 1916, pages 797 to 801) with the exception, of aluminium chloride. Such suitable catalysts are, for example, tin tetrachloride,

zinc chloride, strongsulfuric acid, ferric.

chloride, boro-fluoro acetic acid and antimony pentachloride.

The quantity of the m-substitutedarylalkyl-ether may be varied within the widest limits, but generally I add about 5-25% to the reaction mixture calculated on the amount of the resinifiable substance present in the crude solvent naphtha.

,' In carrying .out the process I add the requisite quantity of the catalyst, generally 0,520% calculated on the amount of the crude solvent naphtha, to the crude solvent naphtha aryl alkyl ether mixture with vigorous stirrlng, care being taken that the reaction C. generally invention, 7

I carry out the process between about 30-70 C., the temperature being regulated by gently heating or cooling. When the reaction is complete generally after several hours, the catalyst is removedby means of acids, alkalies, alkaline earths or metallic oxides and the volatile constituents are distilled ofi completely fromthe filtered resin solution, advantageously with the application of re duced pressure. a

The new resins thus obtained are generally colorless to yellowish colored, substances. They are distinguished by being completely soluble in all proportions in-the commercial benzin'es, even at ordinary temperature and also in drying oils. Due to their valuable solubility properties and their stability to light the new products constitute excellent basic materials for the manufacture of oil lacquers and plastic masses of high quality. Moreover, these resins can be worked up excellently with cellulose ethers to "completely transparent and highly lustrous drying lacquers or with the addition of appropriate softening agents to valuable plastic masses.

According to the nature of the catalyst used the properties of the resins as regards solubility, melting point and color can be modified. Thus, for example by means of tin tetrachloride very light colored resins are obtained, which are not soluble in the socalled stand oils prepared from lean, stored linseed oil by heating (compare Chemical Abstracts, Vol. VI, pp. 3190 and 3192), but dissolve in the customary drying oils. The use of borofluoro acetic acid as catalyst leads to nearly colorless, high melting resins, soluble in stand oils, while, when sulfuric acid is used as catalyst, lower melting resins are formed, which are light brown in color and soluble in stand oils. It is not necessary that the meta-substituted arylal l ethers should be used in a pure state. Tec

meal mixtures of arylalkyl ethers can also .be used, which besides meta substituents (adxylenol mixtures.

When the meta-substituted arylalkyl ethers are replaced completely by the corresponding orthoor para-substituted arylalkyl ethers, resins insoluble in oil and in benzine are obtained. Conversely, when crude solvent naphtha is treated with polymerizing agents without the addition of meta-subsituted arylalkyl ethers, resins are always obtained, which at ordinary temperature are completely or mainly insoluble in aliphatic and ydroaromatic benzines. a

The invention is illustrated by the fol-low-'v in examples, but is not restricted thereto:

trample 1.-1000 parts by weight of a crude solvent naphtha, boiling between 160 and 185 0., free from bases and phenols and containing 54% of resinifiable constituents (cumarone and indene), are mixed with 85 parts by weight of m-xylene-methyl-ether and heated to 32 C.,-then parts by weight of tin tetrachloride are run in gradually with vigorous stirring. The reactiontemperature rises to 50 C. After stirring for 6 hours the reaction mass is diluted with 250 parts b weight of xylene and then stirred for, a out half an hour with about 60 parts by weight of quick lime while heating to 90-100 C. The resin solution is filtered from the precipitate and the volatile constituents distilled off completely in vacuo.

There are obtained 480 parts by weight of a very light colored resin melting at 148 C., which dissolves readily and completely in lacquer benzine, linseed oil and wood oi These solutions remain completely clear, even at a low temperature. 3 q

Ewample 2.- parts by weight ofmolten ferric chloride (FeCl,.6H O) are run gradually with vigorous stirring into a mixture (heated to C.) of 300 parts by. weight ofthe crude solvent naphtha, used 'in Example 1, with 25 parts by weight of m-toluene-methyl-ether. 1

- The temperature rises to about 47 C.v

After stirring for 5 hours the mass is diluted with 100-150 parts by weight of purified solvent naphtha, filtered from solid substances and the filtrate is treated with heating and stirring with a-mixture of 36'parts by weight of activated fullers earth and 18 parts by weightof quick lime. The volatile constituents are distilled oil in vacuo from the filtered solution. There are obtained 153 arts by weight of a light yellow resin, melting at 138 C., readily solublein cyclohexane, aliphatic and hydroaromatic benzines, linseed oil, wood oil and linseed oil--stand oil.

Example 3.In 100 partsby weight of the crude solvent naphtha, used in Example 1,

" aue-47o are dissolved 15 parts by weight of a toluene- I methyl-ether, obtainable by the methylation I same solubility properties as the product 0b tained in Example 2.

Emample 4.A mixture, heated to 0., of 1000 ,parts by weight of.'crude solvent naphtha (limits of boiling point 163182 C., content of cumarone and indene 52% and free from phenols and bases) with.86 parts by weight of m-xylene ethyl-ether is treated as described in Example 3 with 10 parts by weight of borofluoro acetic acid. When the reaction is complete the reaction mass is diluted with 200 parts by weight of xylene or purified solvent naphtha and treated, while hot with 60 parts by weight of calcium oxide or barium oxide."

There are "obtained 545 parts by weight of a nearly colorless resin, which melts at 133 C. and possesses the same solubility. properties as the resin obtainable in accordance with Example2.

- Ewample 5.200 parts by weight-of crude solvent naphthaused in Example 4 are treated with 17 parts by weight of xylene-methylether, obtainable by the'alkylation of a xylenol containing about of m-xylenol. 3 to 5 parts by weight of concentrated sulfuric acid are run very slowly into the mixture at' 15-20 C., whereupon the reaction temperature'rises gradually to 60 C. After stirring for 3 to 5 hours the reaction mass is diluted with 50 parts by weight of a purified solvent naphtha, separated from 'the sulfuric acid.

washed with sodium carbonate solution and then 'with sodium chloride solution. There are obtained 108 parts by weight of a pale brown resin, soluble in benzine and stand oil and melting at 94 C.

Example 6.A mixture of 500 parts by weight of the crude solvent naphtha used in Example 4 with 51 parts by weight-of m-xylene-ethyl-ether is stirred for'5 hours with the gradual addition of a solution of 10 parts by weight of antimony pentachloride in 40-50 parts by weight oftetrachloroethane, whereupon the temperature of the reaction rises from 27 to 57 C. The reaction liquid is then stirred vigorously for half an hour at -100 C. with 40 parts by weight of 32% caustic soda solution. The light colored resin solution is then separated from the sediment.

resinifiable substance in There are obtained 210 parts by weiht of t 1i ht yellow resin, melting at 130 and ;olu le in lacquer benzine, linseed oil and wood oil.

I claim:

1. The proces which comprises stirring a mixture of a crude solvent naphtha and a [ti-substituted arylalkyl ether of the general formula:

R OR

wherein R and R stand for alkyl groups and It stands for hydrogen which may be substituted by an alkyl group, with the addition of a polymerization catalyst of the group consisting of tin tetrachloride, zinc chloride, strong sulfuric acid, ferric chloride, borofluoro acetic acid and antimony pentachloride for several hours.

2. The process which comprises stirring a mixture of a crude solvent naphtha and 5 to 25% calculated on the amount of the resini-- fiable substance in the solvent naphtha of a ,m-substituted arylalkyl ether of the general formula B" OR wherein R and R stand for alkyl groups and R stands for hydrogen which may be substituted by an alkyl group, with the addition of a polymerization catalyst of the group, consisting of tin tetrachloride, zinc chloride, strong sulfuric 'acid, ferric chloride, borofluoro acetic acid and antimony pentachloride for several hours. 7

3. The process which comprises stirrin a mixture of a crude solvent naphtha an a Iii-substituted arylalkyl ethenof the general formula ride for several hours.

of a m-substituted arylalkyl ether of the 7 general formula:

R" OR wherein R anclR stand for alkyl groups and R stands for hydrogen which may be'substituted by an a yl group, with the addition of a polymerization catalyst of the group consisting of tin tetrachloride, zinc chloride,

with the addition strong sulfuric acid, ferric chloride, borofluoro acetic acid and antimony pentachlo- 6. The process which comprises stirring a mixture of a crude solvent naphtha, freed from phenols and bases and 5 to 25% calculated on the amount of the resinifiable sub stance in the solvent naphtha of a' m-substituted arylalkylether of the general formula:

wherein R and R stand for alkyl groups and R stands for hydrogen which may be substitutedby an alkyl group, with the addition of a polymerization catalyst -.of the group consisting of tin tetrachloride, zinc chloride,

wherein R and R stand for alkyl groups and R stands for hydrogen which may be substituted by an alkyl group, 'with the addition of a polymerization catalyst of the group consisting of tin tetrachloride, zinc chloride, strong sulfuric acid, ferric chloride, borofluoro acetic acid and antimony pentachloride for several hours at a temperature below 90 C.

4:. The process which comprises stirringa mixture of a crude solvent naphtha and 5 to 25% calculated on the amountof the the solvent naphtha strong sulfuric acid, ferric chloride, borofluoro acetic acid and antimony pentachloride for several hours.

7. The process mixture of acrude solvent naphtha freed from phenols and bases and of a m-substituted arylalkyl ether of the general formula:

R" OR 1v wherein R and R stand for alkyl groups and R stands for hydrogen which may be substi tuted by an alkyl group, with the addition of which comprises stirring a a polymerization catal st of the grou consisting of tin tetrach oride, zinc ch oride, strong sulfuric acid, ferric chloride, borofluoro acetic acid and antimony pentachloride for several hours at a temperature bewherein R and R stand for alkyl groups and R" stands for hydrogen which may be substituted by an alkyl group, with the addition of a polymerization catalyst of the group consisting of tin tetrachloride, zinc chloride,

strong sulfuric acid, ferric chloride, borofluoro acetic acid and antimony pentachlo-. ride for several hours at a temperature below 9. The process which comprisesstirring a i'mixture' of crude solvent naphtha freed from claim 1, being generall phenols and bases and of a m-substituted arylalkyl ether of the general formulaz.

on. 0cm:

wherein R stands for hydrogen which may be substituted by an alkyl group, with the addition of aborofiuoro acetic acid as catalyst for several; hours at a temperature below 10. The process which comprises stirrin a mixture of crude solvent naphtha freed from phenols and bases and of 5 to 25% calculated on the amount of the resinifiable substance in. the solvent naphtha of m-xylenevcthyl-ether with the addition of borofluoroacetic acid for several hours at a temperature of from'40 to C. s

11. As new products synthetic resinsobtainable according to a process as claimed in colorless toyellowish colored substances an being soluble in commercial benzines and in drying oils,

12. As new products synthetic resins obtainable according to a process as claimed in claim 2, being generally colorless to yellow ish colored substances and being soluble in commercial benzines and in drying oils.

13. As new tainable according tovfl-oprocess as claimed in claim 3, being generally colorless to yellowish colored substances and being soluble in commercial benzines and in drying oils. v

, 14 As new products synthetic resins obtainable accor ish colored su products synthetic resins obtainable according to a process as claimed claim 4, being generall colorless to yellowi colored substances an being soluble in C01 mercial benzines and in drying oils.

15. As new. roducts synthetic resins o tainable according to a process as claimed claim 5, being generally colorless to yelloi ish colored substances and being soluble commercial benzinesand in drying oils.

16. As new products synthetic resins o tainable accordingrto a process as claimed claim 6, being generally colorless to yelloi ish colored substances andbeing soluble 1 commercial benzines and in drying oils.

17. As new products synthetic resins ol ta-inable according to a process as claimed 1' claim 7, being generally colorless to yellov ish colored substances and being soluble i commercial benzines and in drying oils.

18. As new (products synthetic resins 0] ing to a rocess as claime in claim 8, being general y colorless to ye lowish colored substances and being solubl in commercial benzines and in drying oils.

19. As-new roducts synthetic resins ol tainable accor mg to a process as claimed i claim 9, being generally colorless to yellow ish colored substances and being soluble i1 commercial benzines and in drying oils.

20. As new roducts synthetic resins ob tainable accord ing to a process as claimed i1 claim 10, bein generally colorless to yellow stances and being soluble ii commercial benzines and in drying oils.

In testimony whereof I have hereunto so my hand. LEO ROSENTHAL, [L 5.] 

